Boron Dipyrromethene Units Research Articles

Bifunctional luminescent conjugated microporous polymers containing BODIPY and tetraphenylethene units for highly efficient energy storage and enhanced sensing of Cu2+ ions

Here, using the Sonogashira coupling technique, a new fluorescent tetraphenylethene (TPE) and borondipyrromethene (BODIPY)-based CMP (TPE-BODIPY-CMP) was built and developed for usage in supercapacitors and Cu2+ ion detection. XPS, ssNMR, and FTIR techniques were used to validate the presence of the functional groups, aromatic carbons, and atoms [Si, B, C, N, O, and F] in the TPE-BODIPY-CMP framework. In the TPE-BODIPY-CMP, the calculated pore size, SBET, and carbon residue were 1.52–2.82 nm, 300 m2 g−1, and 67%, respectively. as per our electrochemical test, the capacitance stability [83.23% after 5000 cycles], and specific capacity of 176 F g−1 (0.5 A g−1) for TPE-BODIPY-CMP. We performed photoluminescence (PL) experiments on TPE-BODIPY-CMP to evaluate its capacity in cation detection [Cu2+, Pb2+, Al3+, Cr3+, Ni2+, Ce3+, Mg2+, Hg2+, Fe3+, Fe2+, Zn2+, and Ag+] and a limit of detection (LOD) of TPE-BODIPY-CMP toward Cu2+ ions was 2.5 × 10−7 M.

Design, Synthesis, and Characterization of Organometallic BODIPY-Ru(II) Dyads: Redox and Photophysical Properties with Singlet Oxygen Generation Capability†.

A series of Ru(II)-acetylide complexes (Ru1, Ru2, and Ru1m) with alkynyl-functionalized borondipyrromethene (BODIPY) conjugates were designed by varying the position of the linker that connects the BODIPY unit to the Ru(II) metal center through acetylide linkage at either the 2-(Ru1) and 2,6-(Ru2) or the meso-phenyl (Ru1m) position of the BODIPY scaffold. The Ru(II) organometallic complexes were characterized by various spectroscopic methods, including nuclear magnetic resonance (NMR) spectroscopy, infrared (IR) spectroscopy, CHN, and high-resolution mass spectrometry (HRMS) analyses. The Ru(II)-BODIPY conjugates exhibit fascinating electrochemical and photophysical properties. All BODIPY-Ru(II) complexes exhibit strong absorption (εmax = 29,000-72,000 M-1 cm-1) in the visible region (λmax = 502-709 nm). Fluorescence is almost quenched for Ru1 and Ru2, whereas Ru1m shows the residual fluorescence of the corresponding BODIPY core at 517 nm. The application of the BODIPY-Ru(II) dyads as nonporphyrin-based triplet photosensitizers was explored by a method involving the singlet oxygen (1O2)-mediated photo-oxidation of diphenylisobenzofuran. Effective π-conjugation between the BODIPY chromophore and Ru(II) center in the case of Ru1 and Ru2 was found to be necessary to improve intersystem crossing (ISC) and hence the 1O2-sensitizing ability. In addition, electrochemical studies indicate electronic interplay between the metal center and the redox-active BODIPY in the BODIPY-Ru(II) dyads.

Ultrafast Charge Separation Driven by Torsional Motion in Orthogonal Boron Dipyrromethene Dimer

In this work, the photoinduced charge separation (CS) via symmetry breaking in an orthogonal meso-β-linked boron dipyrromethene (BODIPY) dimer was investigated by polarized transient absorption spectroscopy. The time constant about 0.76 ps of the CS reaction determined in dimethyl sulfoxide is much faster than the solvation dynamics. The observed transient anisotropy of the BODIPY anion band implies that both hole and electron transfers occur with similar probabilities. The bidirectional charge transfer processes suggest that the locally excited state is weakly coupled to the polar solvent, and the solvation coupled excited-state structural relaxation within the BODIPY monomeric unit is rather limited. In combination with the electronic excitation analysis based on time-dependent density-functional theory calculations, we deduced that the CS in the orthogonal BODIPY dimer is enabled via the torsional motion associated with covalently connected BODIPY units, promoting the electronic coupling, and irrelevant to the dynamic solvent relaxation.

Nonlinear optical response of some Boron-dipyrromethene dyes: An experimental and theoretical investigation

The nonlinear optical properties of a functional Boron dipyrromethene (BODIPY) derivative, namely BODIPY 1, and its subsequent formed supramolecular romboidal cavitand BODIPY 2(OTf)4, formed by mixing 1 with the 90° platinum triflate Pt(dppp)(OTf)2 linker, were investigated under femtosecond (fs) and picosecond (ps) laser excitation conditions, using the Z-scan (50 fs, 800 nm and 35 ps, 532/1064 nm) and Optical Kerr effect (OKE) (50 fs, 800 nm and 35 ps, 532 nm) techniques. Both BODIPYs exhibited strong nonlinear refractive response (self-defocusing) under both excitation conditions, while they exhibited negligible nonlinear absorptive response under ps excitation and significant reverse saturable absorption under fs excitation. The nonlinear optical response of 2(OTf)4 was found importantly increased compared to 1 under both excitation regimes, due to the more dense electronic spectrum of the BODIPY-metal derivative. The experimental results are compared and discussed with the results obtained from theoretical computations performed using Density Functional Theory (DFT). In fact, the theoretical study showed that the polarization character of the BODIPY unit can be tuned upon functionalization. The theoretical calculations were found to be qualitatively in good agreement with the experimental results, predicting successfully the larger second hyperpolarizability of 2(OTf)4. The present findings are discussed and compared with the results from other similar studies in the literature.

Light-Harvesting Crystals Formed from BODIPY-Proline Biohybrid Conjugates: Antenna Effects and Excitonic Coupling.

A boron dipyrromethene (BODIPY) derivative bearing a cis-proline residue at the meso-position crystallizes in the form of platelets with strong (i.e., ΦF = 0.34) red fluorescence, but the absorption and emission spectra differ markedly from those for dilute solutions. A key building block for the crystal is a pseudo-dimer where hydrogen bonding aligns the proline groups and separates the terminal chromophores by ca. 25 Å. Comparison with a covalently linked bichromophore suggests that one-dimensional (1D) excitonic coupling between the terminals is too small to perturb the optical properties. However, accretion of the pseudo-dimer forms narrow channels possessing a high density of chromophores. The resultant absorption spectrum exhibits strong excitonic splitting, which can be explained quantitatively using the extended dipole approach and allowing for coupling between ca. 30 BODIPY units. Fluorescence, which decays with a lifetime of 2.2 ns, is assigned to a delocalized and (slightly) super-radiant BODIPY dimer situated at the interface and populated via electronic energy transfer from the interior.

BODIPY-Ruthenium(II) Bis-Terpyridine Complexes for Cellular Imaging and Type-I/-II Photodynamic Therapy.

A series of multichromophoric ruthenium(II) complexes with the formulation [Ru(tpy-BODIPY)(tpy-R)]Cl2 (1-4), having a heteroleptic Ru(II)-bis-tpy (tpy = 4'-phenyl-2,2':6',2″-terpyridine) moiety covalently linked to a boron-dipyrromethene (BODIPY) pendant, have been prepared and characterized and their application as a phototherapeutic and photodetection agent in cancer therapy has been explored. Ligand L1 with a terpyridine-BODIPY moiety and complex 1 as its PF6 salt (1a) have been structurally characterized by a single-crystal X-ray diffraction study. Complex 1a has a distorted-octahedral RuN6 core with a Ru(II)-bis-terpyridine unit that is covalently linked to one photoactive BODIPY unit. The complexes exhibit strong absorbance near 502 nm (ε ≈ (3.7-7.8) × 104 M-1 cm-1) and high singlet oxygen sensitization ability, giving singlet oxygen quantum yield (ΦΔ) values ranging from 0.57 to 0.75 in DMSO. An emission-based study using complex 4 and Singlet Oxygen Sensor Green (SOSG) displays the formation of singlet oxygen inside the cells and also in the buffer medium upon light irradiation. DNA (pUC19) photocleavage experiments using ROS scavengers/stabilizers reveal photoinduced generation of singlet oxygen by a type-II process and of the superoxide anion radical by a type-I process. Complex 4 having a pendant biotin moiety as a cancer cell targeting group shows high photocytotoxicity with a remarkable phototherapeutic index (PI) value of >1400 in HeLa cancer cells with a low light dose activation (400-700 nm, 2.2 J cm-2). The complexes display reduced activity in noncancerous HPL1D cells. The emission property of the complexes is used for cellular imaging, thus making them suitable as next-generation theranostic PDT agents.

Tailoring the Solid-State Fluorescence of BODIPY by Supramolecular Assembly with Polyoxometalates.

A cationic boron dipyrromethene (BODIPY) derivative (1+) has been successfully combined with two polyoxometalates (POMs), the Lindqvist-type [W6O19]2- and the β-[Mo8O26]4- units, into three new supramolecular fluorescent materials (1)2[W6O19]·2CH3CN, (1)2[W6O19], and (1)4[Mo8O26]·DMF·H2O. The resulting hybrid compounds have been fully characterized by a combination of single-crystal X-ray diffraction, IR and UV-vis spectroscopies, and photoluminescence analyses. This self-assembly approach prevents any π-π stacking interactions not only between the BODIPY units, responsible for aggregation-caused quenching (ACQ) effects, but also between the BODIPY and the POMs, avoiding intermolecular charge-transfer effects. Noticeably, the POM units do not only act as bulky spacers, but their negative charge density drives the molecular arrangement of the 1+ luminophore, strongly modifying its fluorescence in the solid state. As a consequence, the 1+ cations are organized into dimers in (1)2[W6O19]·2CH3CN and (1)2[W6O19], which are weakly emissive at room temperature, and in a more compact layered assembly in (1)4[Mo8O26]·DMF·H2O, which exhibits a red-shifted and intense emission upon similar photoexcitation.

BODIPY-attached zinc(II) complexes of curcumin drug for visible light assisted photo-sensitization, cellular imaging and targeted PDT.

Boron-dipyrromethene (BODIPY) based photosensitizers as porphyrinoids and curcumin as natural product possess exciting photophysical features suitable for theranostic applications, namely, imaging and photodynamic therapy (PDT). Limited aqueous solubility and insufficient physiological stability, however, reduce their efficacy significantly. We have designed a novel strategy to deliver these two unusable cytotoxins simultaneously in cancer cells and herein, report the synthesis, characterization and imaging-assisted photocytotoxicity of three zinc(II) complexes containing N3-donor dipicolylamine (dpa) ligands (L1-3) and O,O-donor curcumin (Hcur) viz. [Zn(L1)(cur)]Cl (1), [Zn(L2)(cur)]Cl (2) and [Zn(L3)(cur)]Cl (3), where L2 and L3 have pendant fluorescent BODIPY and non-emissive di-iodo-BODIPY moieties. Metal chelation imparted remarkable biological stability (pH ∼7.4) to the respective ligands and induces significant aqueous solubility. These ternary complexes could act as replacements of the existing metalloporphyrin-based PDT photosensitizers as their visible-light photosensitizing ability is reinforced by the dual presence of blue light absorbing curcumin and green light harvesting BODIPY units. Complex 2 having emissive BODIPY unit L2 and curcumin, showed mitochondria selective localization in HeLa, MCF-7 cancer cells and complex 3, the di-iodinated analogue of complex 2, exhibited type-I/II PDT activity via inducing apoptosis through mitochondrial membrane disruption in cancer cells while being significantly nontoxic in dark and to the healthy cells.

Fully-water-soluble BODIPY containing fluorescent polymers prepared by RAFT method for the detection of Fe3+ ions

The development of water-soluble polymer dyes is of great practical and scientific significance. In this article, small fluorescent molecule boron-dipyrromethene (BODIPY) bearing C=C bond was synthesized first. And then, via Suzuki reaction, recognition groups were introduced into the 2, 6 positions of BODIPY. Thus polymerizable fluorescent monomers were prepared. Finally, methacrylic acid (MAA) was copolymerized with the as-prepared small molecular fluorescent monomers via reversible addition-fragmentation chain transfer (RAFT) polymerization methodology. Four fully-water-soluble polymer sensors with BODIPY moieties in the end of the polymer chain were obtained eventually. In the presence of long PMAA chain, and by the assistance of it, BODIPY could be dissolved totally in water. These polymer sensors exhibited sensitive and selective recognition ability to Fe3+. Even the content rate of BODIPY was as low as 0.5% of the polymer (calculated from element analysis), the detection limit could reach 1.2 μM. The sensors with two recognition groups in one BODIPY unit were more sensitive than that with one recognition groups in each BODIPY unit. The sensing mechanism was investigated as well. By endowing the water solubility to organic sensors, the application scope could be greatly enlarged in sensing metal ions in aqueous environments. This work provides a method to develop water soluble high performance polymer sensors.

Ultrafast Electron/Energy Transfer and Intersystem Crossing Mechanisms in BODIPY-Porphyrin Compounds

Meso-substituted borondipyrromethene (BODIPY)-porphyrin compounds that include free base porphyrin with two different numbers of BODIPY groups (BDP-TTP and 3BDP-TTP) were designed and synthesized to analyze intramolecular energy transfer mechanisms of meso-substituted BODIPY-porphyrin dyads and the effect of the different numbers of BODIPY groups connected to free-base porphyrin on the energy transfer mechanism. Absorption spectra of BODIPY-porphyrin conjugates showed wide absorption features in the visible region, and that is highly valuable to increase light-harvesting efficiency. Fluorescence spectra of the studied compounds proved that BODIPY emission intensity decreased upon the photoexcitation of the BODIPY core, due to the energy transfer from BODIPY unit to porphyrin. In addition, ultrafast pump-probe spectroscopy measurements indicated that the energy transfer of the 3BDP-TTP compound (about 3 ps) is faster than the BDP-TTP compound (about 22 ps). Since the BODIPY core directly binds to the porphyrin unit, rapid energy transfer was seen for both compounds. Thus, the energy transfer rate increased with an increasing number of BODIPY moiety connected to free-base porphyrin.

Efficient energy transfer in phenyl-ethynyl-linked asymmetric BODIPY dimers

Abstract Three asymmetric boron dipyrromethene (BODIPY) dimers were synthesized via coupling of a BODIPY monomer with a meso-phenyl ethynyl group substituent to the different monomers with an iodine atom at the second position of the BODIPY core. The dimers were characterized by 1H, 13C, and 11B, 19F NMR spectroscopy and high-resolution mass spectrometry. Density functional theory calculations show minimal conjugation between the two BODIPY units in the dimers due to a large dihedral angle between the BODIPYs and the linker. Absorption and fluorescence measurements of monomeric and dimeric compounds in dichloromethane indicated highly efficient singlet-singlet energy transfer between two BODIPY units (in which the meso-phenyl containing BODIPY unit act as the donor while the other BODIPY unit is the acceptor) and large Stokes shifts. In particular, the dimer with the styryl BODIPY unit absorbs light in a wide range of the spectrum (325 nm–690 nm) with emission in the near IR region. The ethynyl thiophene linked dimer showed the highest fluorescence quantum yield (76%) of all three dimers investigated in this study.

Macrocyclic Arenes Functionalized with BODIPY: Rising Stars among Chemosensors and Smart Materials

Macrocycles play a crucial role in supramolecular chemistry and the family of macrocyclic arenes represents one of the most important types of hosts. Among them, calixarenes, resorcinarenes and pillararenes are the most commonly encountered macrocyclic arenes, and they have received considerable attention. Boron-dipyrromethene (BODIPY) dyes are fascinating compounds with multiple functionalization sites and outstanding luminescence properties including high fluorescence quantum yields, large molar absorption coefficients and remarkable photo- and chemical stability. The combination of macrocyclic arenes and BODIPY dyes has been demonstrated to be an effective strategy to construct chemosensors for various guests and smart materials with tailored properties. Herein, we firstly summarize the recent advances made so far in macrocyclic arenes substituted with BODIPY. This review only focuses on the three macrocyclic arenes of calixarenes, resorcinarenes and pillararenes, as there are no other macrocyclic arenes substituted BODIPY units at the present time. Hopefully, this review will not only afford a guide and useful information for those who are interested in developing novel chemosensors and smart materials, but also inspire new opportunities in this field.

Electron-Withdrawing Boron Dipyrromethene Dyes As Visible Light Absorber/Sensitizers on Semiconductor Oxide Surfaces.

The synthesis, characterization, and electrochemical and photophysical properties of the phosphonate-derivatized carbazole (CBZ) and boron dipyrromethene (BODIPY) chromophores in the dyes, BODIPY(CBZ)2PO3H2 (8) and BODIPY(Tol)2PO3H2 (7), are described. The oxide-bound dyes have been explored as light absorbers in dye-sensitized photoelectrosynthesis cell (DSPEC) applications. The BODIPY-CBZ phosphonate ester (6) features a broad, intense UV-visible absorption spectrum with absorptions at 297 and 650 nm that arise from mixed transitions at the CBZ and BODIPY units. Electrochemical measurements on BODIPY(CBZ)2Br (4) in 0.1 M [nBu4N][PF6] in dichloromethane, vs normal hydrogen electrode (NHE), reveal reversible oxidations at 1.19 and 1.41 V and a reversible reduction at -0.59 V. On indium tin oxide (ITO) and TiO2, a reversible one-electron oxidation appears for 7 at 0.86 and 0.90 V vs NHE in dichloromethane, respectively, which demonstrates the redox stability on metal oxide surfaces. The results of nanosecond transient absorption measurements on SnO2/TiO2 electrodes provide direct evidence for excited-state electron injection into the conduction band of TiO2 following 590 nm excitation. A longer lifetime for 8+ compared to 7+ is consistent with extensive intramolecular charge separation between the CBZ and BODIPY units on the surface. Photoelectrochemical studies on 8 on a SnO2/TiO2 photoanode resulted in sustained photocurrents with current maxima of ∼200 μA/cm2 with hydroquinone added as a reductant under 1 sun (AM1.5 100 mW·cm-2) illumination at pH 4.5 in 0.1 M acetate buffer and 0.4 M LiClO4. On mixed SnO2/TiO2 electrode surfaces, with the added catalyst [Ru(Mebimpy)((4,4'-(OH)2PO-CH2)2bpy)(OH2)]2+ and chromophores 7 and 8, addition of 0.1 M benzyl alcohol resulted in sustained photocurrents of 12 and 35 μA/cm2, consistent with oxidation to benzaldehyde.

Cyclotriphosphazene cored naphthalimide-BODIPY dendrimeric systems: Synthesis, photophysical and antimicrobial properties

In this work, we report the synthesis and characterization of novel fluorescent naphthalimide (NI)-boron dipyrromethene (BODIPY) dyads and dendrimeric triad systems, based on NI functionalized mono- and distyryl- BODIPY derivatives with cyclotriphosphazene core. The structures of new dyads and triad systems were characterized by 1H, 13C and 31P NMR. Spectroscopic properties including absorption, emission profiles, fluorescence quantum yield and fluorescence lifetime of NI-BODIPY dyads and NI-BODIPY-cyclotriphosphazene triads were investigated via UV–Vis absorption and fluorescence emission (2D and 3D) techniques. The NI groups on BODIPYs 3- and 5-positions procure the red-shift in absorption and emission spectra compared to BODIPY core. The energy transfer process inhibited the emission of NI moiety and induced the fluorescence from BODIPY unit. The dendrimeric mono- and di-styryl NI-BODIPY-cyclotriphosphazene systems (7 and 8) presented intense absorption bands about 570 and 639 nm respectively both excited from NI and BODIPY subunits. Also, the triad systems (7 and 8) were screened against Gram-positive and Gram-negative bacterial strains. The results demonstrated that naphthalimide-BODIPY-cyclotriphosphazene triads had an antimicrobial activity against Gram-positive Staphylococcus aureus.

Diplatinum(II) Catecholate of Photoactive Boron-Dipyrromethene for Lysosome-Targeted Photodynamic Therapy in Red Light.

The binuclear platinum(II) boron-dipyrromethene (BODIPY) complex [{Pt(dach)}2(μ-Dcrb)] (DP), where dach is 1,2-diaminocyclohexane and H4Dcrb is a morpholine-conjugated BODIPY-linked dicatechol bridging ligand, was prepared for lysosome organelle targeting and near-IR (NIR) light (600-720 nm) induced photocytotoxic activity. The platinum complex [Pt(dach)(cat)] (CP), where H2cat is catechol, was synthesized and used as a control complex without bearing the BODIPY unit. The complex DP displayed a band at 660 nm (ε = 2.1 × 104 M-1 cm-1) in the red region of the UV-visible spectrum recorded in 10% dimethyl sulfoxide/Dulbecco's Modified Eagle's Medium (DMSO/DMEM, pH 7.2). The complex DP and the BODIPY ligand displayed emission in 10% DMSO-DMEM (pH 7.2) giving an λem value of 668 nm (λex = 650 nm) with a ΦF value of 0.02 for DP and 0.16 for H4Dcrb (ΦF, fluorescence quantum yield). Titration experiments using 1,3-diphenylisobenzofuran (DPBF) indicated that the complex DP and H4Dcrb on irradiation with near-IR light of 600-720 nm generated singlet oxygen (1O2) as the ROS (reactive oxygen species). The complex DP showed significant lysosomal localization and remarkable apoptotic photodynamic therapy (PDT) effects, giving half-maximal inhibitory concentration values (IC50) within 0.6-3.4 μM in HeLa cervical cancer, A549 lung cancer, and MDA-MB231 multidrug resistant cancer cells, while being essentially nontoxic in the dark and in the HPL1D immortalized lung epithelial normal cells. The acridine orange assay using A549 cells showed lysosomal membrane permeabilization by the complex DP under near-IR light (600-720 nm). This complex on near-IR light (600-720 nm) activation in A549 cells induced apoptotic cell death, as observed from an Annexin-V FITC assay.

Construction of cathepsin B-responsive fluorescent probe and photosensitizer using a ferrocenyl boron dipyrromethene dark quencher

A ferrocenyl boron dipyrromethene (BODIPY) has been developed and utilized as a dark quencher to construct a cathepsin B-responsive fluorescent probe and photosensitizer. The smart fluorescent probe and photosensitizer (Pc-FcQ) contains a zinc(II) phthalocyanine as the fluorescent and photosensitizing unit which is conjugated to the ferrocenyl BODIPY dark quencher via a cathepsin B-cleavable peptide substrate [Gly-Phe-Leu-Gly-Lys]. The photosensitizing properties of Pc-FcQ, including fluorescence and singlet oxygen generation, are significantly quenched through energy transfer to the BODIPY unit and subsequently by the photoinduced electron transfer from the nearby ferrocenyl moiety. Upon exposure of cathepsin B in human hepatocellular carcinoma HepG cells, the fluorescence emission of Pc-FcQ could be restored, indicating the cleavage of the peptide substrate and the separation of the phthalocyanine and ferrocenyl BODIPY unit. However, the intracellular fluorescence intensity of Pc-FcQ was largely diminished after the cells were pre-treated with cathepsin B inhibitor. Its intracellular fluorescence intensity was comparable to that of the control compound in which the peptide substrate was replaced by the non-cleavable one [Gly-Gly-Gly-Gly-Lys]. The singlet oxygen generation of Pc-FcQ was also examined in HepG2 cells as reflected by the cytotoxicity assay. The Pc-FcQ exhibited higher potency when compared with the non-cleavable analogue due to the cleavage of peptide substrate and the detachment of the BODIPY dark quencher from the phthalocyanine. The activation of the Pc-FcQ was also demonstrated in tumor-bearing nude mice. After intratumoral injection of Pc-FcQ, the fluorescence intensity at the tumor region increased gradually over 10 h as a result of the detachment of the dark quencher upon the action of cathepsin B. All the results suggest that this ferrocenyl BODIPY could serve as an efficient dark quencher and the resulting Pc-FcQ could act as the cathepsin B-responsive fluorescent probe and activatable photosensitizer.

A Phthalocyanine‐Based Glutathione‐Activated Photosensitizer with a Ferrocenyl Boron Dipyrromethene Dark Quencher for Photodynamic Therapy

AbstractAn efficient near‐infrared‐absorbing dark quencher based on ferrocenyl boron dipyrromethene (BODIPY) has been developed and used to construct a fluorescence resonance energy transfer (FRET)‐based activatable photosensitizer. This smart photosensitizer contains a zinc(II) phthalocyanine as the photosensitizing unit which is conjugated to this dark quencher through a glutathione‐cleavable disulfide linker. The photoactivities of the phthalocyanine unit are largely quenched through FRET to the BODIPY unit followed by photoinduced electron transfer from the attached ferrocenyl moiety. Upon exposure to glutathione in phosphate buffered saline and inside HT29 human colorectal adenocarcinoma cells, the fluorescence emission and singlet oxygen generation efficiency of the photosensitizer are significantly enhanced due to cleavage of the disulfide bond and detachment of the dark quencher from the photosensitizing unit. The activation in fluorescence emission has also been demonstrated in tumor‐bearing nude mice. The glutathione‐responsive behavior has been verified by comparison with the negative results of a non‐cleavable analogue. The results suggest that ferrocenyl BODIPYs could serve as tailorable dark quenchers and the disulfide‐linked phthalocyanine–quencher conjugate acts as an efficient glutathione‐activated photosensitizer for photodynamic therapy.

A Malonyl-Based Scaffold for Conjugatable Multivalent Carbohydrate-BODIPY Presentations.

A concise synthetic route from methylmalonate to a tetravalent aliphatic scaffold has been developed. The ensuing tetra-tethered derivative is equipped with two hydroxyl groups, as well as orthogonal alkene and alkyne functionalities. The usefulness of the scaffold has been demonstrated with the preparation of two representative multivalent derivatives: (i) a tetravalent compound containing two D-mannose units, one fluorescent boron-dipyrromethene (BODIPY) dye and a suitably functionalized amino acid and (ii) by way of dimerization and saponification, a water-soluble tetramannan derivative containing two fluorescent BODIPY units. Additionally, photophysical measurements conducted on these derivatives support the viability of the herein designed single and double BODIPY-labeled carbohydrate-based clusters as fluorescent markers.

Impact of Ferrocene Substitution on the Electronic Properties of BODIPY Derivatives and Analogues

Bis(ferrocenyl)-functionalized boron dipyrromethene (BODIPY) compound 1 featuring direct Fc-B bonds was obtained via a "prefunctionalization strategy". UV-vis absorption, electrochemical, and transient absorption experiments were performed on compound 1 and its analogues to examine the impact of ferrocenyl substitution on the electronic properties. The ferrocene units were found to have little impact on the absorption spectrum of the BODIPY unit but significantly change the excited-state dynamics.

Syntheses, Spectroscopic Properties, and Computational Study of ( E, Z)-Ethenyl and Ethynyl-Linked BODIPYs.

A series of ( E, Z)-ethenyl- and ethynyl-linked boron dipyrromethene (BODIPY) dimers were synthesized in 23-34% yields by condensation of pyrroles with the corresponding bis-benzaldehydes, followed by oxidation and boron complexation. The BODIPY dimers were characterized by 1H, 13C, and 11B NMR spectroscopy, high-resolution mass spectrometry, and, in the cases of 1b, 2, and 3, by X-ray crystallography. The spectroscopic properties for this series of dimers were investigated in tetrahydrofuran solutions, and very similar absorption and emission profiles were observed for all dimers. Density functional theory calculations show minimal conjugation between the two BODIPY units in the dimers, as a result of the large dihedral angle between the BODIPYs and the linker. The ( E)-ethenyl-linked dimer 1a showed the highest fluorescence quantum yield of all dimers investigated in this study.